The phase morphology and rheological properties of a series of poly(methyl methacrylate)-block-poly(isooctyl acrylate)-block-poly(methyl methacrylate) triblock copolymers (MIM) have been studied. These ... [more ▼]

The phase morphology and rheological properties of a series of poly(methyl methacrylate)-block-poly(isooctyl acrylate)-block-poly(methyl methacrylate) triblock copolymers (MIM) have been studied. These copolymers have well-defined molecular structures, with a molecular weight (MW) of poly(methyl methacrylate) (PMMA) in the range of 3 500-50 000 and MW of poly(isooctyl acrylate) (PIOA) ranging from 100 000 to 140 000. Atomic force microscopy with phase detection imaging has shown a two-phase morphology for all the MIM copolymers. The typical spherical, cylindrical, and lamellar phase morphologies have been observed depending on the copolymer composition. MIM consisting of very short PMMA end blocks (MW 3 500-5 000) behave as thermoplastic elastomers (TPEs), with however an upper-service temperature higher than the traditional polystyrene-block-polyisoprene-block-polystyrene TPEs (Kraton D1107). A higher processing temperature is also noted, consistent with the higher viscosity of PMMA compared to PS. [less ▲]

Poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) triblock copolymers have been prepared by ligated anionic polymerization (LAP; 8K-50K-8K) and atom transfer radical polymerization (ATRP; 9K-51K-9K). Size exclusion chromatography, nuclear magnetic resonance, and differential scanning calorimetry have confirmed that the molecular structure of the two triblock copolymers is essentially identical. However, important differences are found in dynamic mechanical properties, viscoelastic properties, and stress−strain behavior. Indeed, the ATRP copolymer has low storage modulus, high complex viscosity, high order−disorder transition temperature, and poor ultimate tensile strength and elongation at break, compared to those of the LAP analogue. Marked differences also observed by tapping mode atomic force microscopy in the microscopic morphology of thin films of these copolymers. All these observations can be explained by the slow initiation of MMA by the poly(n-butyl acrylate) macroinitiator used in ATRP in contrast to what happens when MMA is added to living poly(tert-butyl acrylate) anions. As a result, the polydispersity of the short poly(methyl methacrylate) (PMMA) outer blocks is much broader in the ATRP copolymer, although the polydispersity index of the triblock is only 1.15. This heterogeneous structure of the ATRP triblock is also supported by the comparison of homo-PMMAs prepared by LAP and ATRP. [less ▲]

Copolymers of N-vinylbenzyl N-methyl pyrrolidinium chloride (VBMPC) and methyl methacrylate, PVBMPC-co-poly(methyl methacrylate) (PMMA), were synthesized by free-radical copolymerization and proved to be prone to crosslinking as a result of the reaction of methyl ester groups with benzyl methyl pyrrolidinium chloride (BMPC) moieties at temperatures higher than 110 °C. When the VBMPC content was lower than 20 wt %, these copolymers were miscible with homo-PMMA. Blends of homo-PMMA and PVBMPC-co-PMMA fully could be cured above 150 °C, when the molecular weight of PMMA exceeded 10,000 and the VBMPC content of the copolymer was higher than 5 wt %. This reaction was carried out to crosslink selectively the PMMA microdomains of PMMA-b-poly(isooctyl acrylate) (PIOA)-b-PMMA (MIM) triblock copolymers to explain the mechanism for the mechanical failure of fully (meth)acrylic thermoplastic elastomers. Comparison of the ultimate tensile properties of MIM block copolymers, when the dispersed PMMA phases and PIOA matrix were crosslinked, led to the conclusion that the ductile failure of the hard PMMA microdomains rather than the elastic failure of the PIOA matrix was the reason for the mechanical failure of MIM triblocks. [less ▲]